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AIE-active polymers via copper mediated reversible deactivation radical polymerization
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Ma, Congkai (2022) AIE-active polymers via copper mediated reversible deactivation radical polymerization. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3909576
Abstract
Molecular aggregation had been regarded to be detrimental to luminescence due to aggregation-caused quenching (ACQ) phenomenon. Intriguingly, the concept of aggregation-induced emission (AIE) has revolutionarily demonstrated that aggregation allows for boosted light emission with an appropriate chemical moiety, contributing potential applications. However, there is a requirement for the development of facile synthesis of well-defined and narrow-dispersed AIE polymers.
As a robust polymerization technique, Cu(0)-mediated reversible deactivation radical polymerization (Cu(0)-RDRP) allows good control over diverse molecular weight, topology and chain length distributions under mild conditions. In this work, 3 different Cu(0)-RDRP techniques are extensively applied to generate well-defined AIE-active polymers by using an AIE-containing initiator tetraphenylethene bromoisobutyrate (TPEBIB). These synthesized TPE-terminated polymers with a range of molecular weights and diverse architectures are all demonstrated to be AIE-active, possessing narrow molar mass distributions and high end-group fidelity at high monomer conversions. This control also provides facile access to in situ generation of block copolymers.
In chapter 2, Cu(0)-wire mediated RDRP was firstly employed for the construction of different polyacrylates. Some copolymers can self-assemble in aqueous media forming fluorescent nanoparticles with various sizes, which can work as lysosome-specific probes in biological imaging.
In chapter 3, aqueous Cu-mediated RDRP with pre-disproportionation of Cu(I) was optimized to provide facile and rapid access to water-soluble AIE polyacrylamides at sub ambient temperatures. Some thermoresponsive polymers can spontaneously self assembled into fluorescent nanoparticles with a suitable size at physiological conditions, applicable for lysosome-specific cell imaging.
Broad interest in light-mediated RDRP arises as it allows for spatial and temporal control over reaction kinetics, monomer sequences and compositions. In chapter 4, we present the synthesis of AIE-active polymers involving >20 different monomers with diverse architectures initiated by TPEBIB using visible-light regulated RDRP in both batch and flow reactors. These AIE-active polymers exhibit good photo-patterning, making them promising materials for advanced optoelectronic device.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Aggregation (Chemistry), Polymers, Addition polymerization, Catalyst poisoning, Copper catalysts | ||||
Official Date: | December 2022 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Haddleton, David M. | ||||
Sponsors: | University of Warwick ; China Scholarship Council | ||||
Format of File: | |||||
Extent: | xviii, 239 pages : colour illustrations, charts | ||||
Language: | eng |
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